Organometal catalyst compositions

ABSTRACT

This invention provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer. This invention also provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer, wherein said catalyst composition comprises a post-contacted organometal compound, a post-contacted organoaluminum compound, and a post-contacted fluorided solid oxide compound.

FIELD OF THE INVENTION

[0001] This invention is related to the field of organometal catalystcompositions.

BACKGROUND OF THE INVENTION

[0002] The production of polymers is a multi-billion dollar business.This business produces billions of pounds of polymers each year.Millions of dollars have been spent on developing technologies that canadd value to this business.

[0003] One of these technologies is called metallocene catalysttechnology. Metallocene catalysts have been known since about 1960.However, their low productivity did not allow them to be commercialized.About 1975, it was discovered that contacting one part water with twoparts trimethylaluminum to form methyl aluminoxane, and then contactingsuch methyl aluminoxane with a metallocene compound, formed ametallocene catalyst that had greater activity. However, it was soonrealized that large amounts of expensive methyl aluminoxane were neededto form an active metallocene catalyst. This has been a significantimpediment to the commercialization of metallocene catalysts.

[0004] Borate compounds have been use in place of large amounts ofmethyl aluminoxane. However, this is not satisfactory, since boratecompounds are very sensitive to poisons and decomposition, and can alsobe very expensive.

[0005] It should also be noted that having a heterogeneous catalyst isimportant. This is because heterogeneous catalysts are required for mostmodern commercial polymerization processes. Furthermore, heterogeneouscatalysts can lead to the formation of substantially uniform polymerparticles that have a high bulk density. These types of substantiallyuniformed particles are desirable because they improve the efficiency ofpolymer production and transportation. Efforts have been made to produceheterogeneous metallocene catalysts; however, these catalysts have notbeen entirely satisfactory.

[0006] Therefore, there is a need in the polymer industry to provide aneconomic material to activate metallocene catalysts, and there is also aneed for efficient heterogeneous metallocene catalysts. The inventorsprovide this invention to help solve these problems.

SUMMARY OF THE INVENTION

[0007] An object of this invention is to provide a process that producesa catalyst composition that can be used to polymerize at least onemonomer to produce a polymer.

[0008] Another object of this invention is to provide the catalystcomposition.

[0009] Another object of this invention is to provide a processcomprising contacting at least one monomer and the catalyst compositionunder polymerization conditions to produce the polymer.

[0010] Another object of this invention is to provide an article thatcomprises the polymer produced with the catalyst composition of thisinvention.

[0011] In accordance with one embodiment of this invention, a process toproduce a catalyst composition is provided. The process comprises (oroptionally, “consists essentially of”, or “consists of”) contacting anorganometal compound, an organoaluminum compound, and a fluorided solidoxide compound;

[0012] wherein said organometal compound has the following generalformula:

(X¹)(X²)(X³)(X⁴)M¹

[0013] wherein M¹ is selected from the group consisting of titanium,zirconium, and hafnium;

[0014] wherein (X¹) is independently selected from the group consistingof cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls;

[0015] wherein substituents on the substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls of (X¹) are selectedfrom the group consisting of aliphatic groups, cyclic groups,combinations of aliphatic and cyclic groups, silyl groups, alkyl halidegroups, halides, organometallic groups, phosphorus groups, nitrogengroups, silicon, phosphorus, boron, germanium, and hydrogen;

[0016] wherein at least one substituent on (X¹) can be a bridging groupwhich connects (X¹) and (X²);

[0017] wherein (X³) and (X⁴) are independently selected from the groupconsisting of halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;

[0018] wherein (X²) is selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, substituted fluorenyls, halides, aliphatic groups,substituted aliphatic groups, cyclic groups, substituted cyclic groups,combinations of aliphatic groups and cyclic groups, combinations ofsubstituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic groups and substituted cyclic groups, amidogroups, substituted amido groups, phosphido groups, substitutedphosphido groups, alkyloxide groups, substituted alkyloxide groups,aryloxide groups, substituted aryloxide groups, organometallic groups,and substituted organometallic groups;

[0019] wherein substituents on (X²) are selected from the groupconsisting of aliphatic groups, cyclic groups, combinations of aliphaticgroups and cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen;

[0020] wherein at least one substituent on (X²) can be a bridging groupwhich connects (X¹) and (X²);

[0021] wherein the organoaluminum compound has the following generalformula:

Al(X⁵)_(n)(X⁶)_(3−n)

[0022] wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbonatoms;

[0023] wherein (X⁶) is a halide, hydride, or alkoxide; and

[0024] wherein “n” is a number from 1 to 3 inclusive;

[0025] wherein the fluorided solid oxide compound comprises fluoride anda solid oxide compound;

[0026] wherein the solid oxide compound is selected from the groupconsisting of silica-titania and silica zirconia.

[0027] In accordance with another embodiment of this invention, aprocess is provided comprising contacting at least one monomer and thecatalyst composition under polymerization conditions to produce apolymer.

[0028] In accordance with another embodiment of this invention, anarticle is provided. The article comprises the polymer produced inaccordance with this invention.

[0029] These objects, and other objects, will become more apparent tothose with ordinary skill in the art after reading this disclosure.

DETAILED DESCRIPTION OF THE INVENTION

[0030] Organometal compounds used in this invention have the followinggeneral formula:

(X¹)(X²)(X³)(X⁴)M¹

[0031] In this formula, M¹ is selected from the group consisting oftitanium, zirconium, and hafnium. Currently, it is most preferred whenM¹ is zirconium.

[0032] In this formula, (X¹) is independently selected from the groupconsisting of (hereafter “Group OMC-I”) cyclopentadienyls, indenyls,fluorenyls, substituted cyclopentadienyls, substituted indenyls, suchas, for example, tetrahydroindenyls, and substituted fluorenyls, suchas, for example, octahydrofluorenyls.

[0033] Substituents on the substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls of (X¹) can be selectedindependently from the group consisting of aliphatic groups, cyclicgroups, combinations of aliphatic and cyclic groups, silyl groups, alkylhalide groups, halides, organometallic groups, phosphorus groups,nitrogen groups, silicon, phosphorus, boron, germanium, and hydrogen, aslong as these groups do not substantially, and adversely, affect thepolymerization activity of the catalyst composition.

[0034] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes.Substituted silyl groups include, but are not limited to, alkylsilylgroups where each alkyl group contains from 1 to about 12 carbon atoms,arylsilyl groups, and arylalkylsilyl groups. Suitable alkyl halidegroups have alkyl groups with 1 to about 12 carbon atoms. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

[0035] Suitable examples of such substituents are methyl, ethyl, propyl,butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl,octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl,chloro, bromo, iodo, trimethylsilyl, and phenyloctylsilyl.

[0036] In this formula, (X³) and (X⁴) are independently selected fromthe group consisting of (hereafter “Group OMC-II”) halides, aliphaticgroups, substituted aliphatic groups, cyclic groups, substituted cyclicgroups, combinations of aliphatic groups and cyclic groups, combinationsof substituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic and substituted cyclic groups, amido groups,substituted amido groups, phosphido groups, substituted phosphidogroups, alkyloxide groups, substituted alkyloxide groups, aryloxidegroups, substituted aryloxide groups, organometallic groups, andsubstituted organometallic groups, as long as these groups do notsubstantially, and adversely, affect the polymerization activity of thecatalyst composition.

[0037] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes.Currently, it is preferred when (X³) and (X⁴) are selected from thegroup consisting of halides and hydrocarbyls, where such hydrocarbylshave from 1 to about 10 carbon atoms. However, it is most preferred when(X³) and (X⁴) are selected from the group consisting of fluoro, chloro,and methyl.

[0038] In this formula, (X²) can be selected from either Group OMC-I orGroup OMC-II.

[0039] At least one substituent on (X¹) or (X²) can be a bridging groupthat connects (X¹) and (X²), as long as the bridging group does notsubstantially, and adversely, affect the activity of the catalystcomposition. Suitable bridging groups include, but are not limited to,aliphatic groups, cyclic groups, combinations of aliphatic groups andcyclic groups, phosphorous groups, nitrogen groups, organometallicgroups, silicon, phosphorus, boron, and germanium.

[0040] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

[0041] Various processes are known to make these organometal compounds.See, for example, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305;5,401,817; 5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636;5,565,592; 5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284;5,554,795; 5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203;5,654,454; 5,705,579; and 5,668,230; the entire disclosures of which arehereby incorporated by reference.

[0042] Specific examples of such organometal compounds are as follows:

[0043] bis(cyclopentadienyl)hafnium dichloride;

[0044] bis(cyclopentadienyl)zirconium dichloride;

[0045] 1,2-ethanediylbis(η⁵-1-indenyl)di-n-butoxyhafnium;

[0046] 1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium;

[0047] 3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafniumdichloride;

[0048] methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

[0049] bis(n-butylcyclopentadienyl)bis(di-t-butylamido)hafnium;

[0050] bis(n-butylcyclopentadienyl)zirconium dichloride;

[0051] dimethylsilylbis(1-indenyl)zirconium dichloride;

[0052] octylphenylsilylbis(1-indenyl)hafnium dichloride;

[0053] dimethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

[0054] dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride;

[0055] 1,2-ethanediylbis(9-fluorenyl)zirconium dichloride;

[0056] indenyl diethoxy titanium(IV) chloride;

[0057] (isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride;

[0058] bis(pentamethylcyclopentadienyl)zirconium dichloride;

[0059] bis(indenyl)zirconium dichloride;

[0060] methyloctylsilyl bis(9-fluorenyl)zirconium dichloride;

[0061] bis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate

[0062] Preferably, said organometal compound is selected from the groupconsisting of

[0063] bis(n-butylcyclopentadienyl)zirconium dichloride;

[0064] bis(indenyl)zirconium dichloride;

[0065] dimethylsilylbis(1-indenyl)zirconium dichloride;

[0066] methyloctylsilylbis(9-fluorenyl)zirconium dichloride

[0067] Organoaluminum compounds have the following general formula:

Al(X⁵)_(n)(X⁶)_(3−n)

[0068] In this formula, (X⁵) is a hydrocarbyl having from 1 to about 20carbon atoms. Currently, it is preferred when (X⁵) is an alkyl havingfrom 1 to 10 carbon atoms. However, it is most preferred when (X⁵) isselected from the group consisting of methyl, ethyl, propyl, butyl, andisobutyl.

[0069] In this formula, (X⁶) is a halide, hydride, or alkoxide.Currently, it is preferred when (X⁶) is independently selected from thegroup consisting of fluoro and chloro. However, it is most preferredwhen (X⁶) is chloro.

[0070] In this formula, “n” is a number from 1 to 3 inclusive. However,it is preferred when “n” is 3.

[0071] Examples of such compounds are as follows:

[0072] trimethylaluminum;

[0073] triethylaluminum (TEA);

[0074] tripropylaluminum;

[0075] diethylaluminum ethoxide;

[0076] tributylaluminum;

[0077] trisobutylaluminum hydride;

[0078] triisobutylaluminum;

[0079] diisobutylaluminum hydride; and

[0080] diethylaluminum chloride.

[0081] Currently, TEA is preferred.

[0082] The fluorided solid oxide compound comprises fluoride and a solidoxide compound. The solid oxide compound is selected from the groupconsisting of silica-titania and silica-zirconia. Silica is the majoritycomponent of the solid oxide compound.

[0083] The titania content of the silica-titania generally ranges fromabout 0.5% to about 30% by weight titanium, preferably, from about 2.5%to about 15% by weight titanium, and most preferably, from 4 to 10% byweight titanium.

[0084] The zirconia content of the silica-zirconia generally ranges fromabout 1% to about 40% by weight zirconium, preferably, from about 5% toabout 30% by weight zirconium, and most preferably, from 8 to 20% byweight zirconium.

[0085] The solid oxide compound should have a pore volume greater thanabout 0.5 cc/g, preferably greater than about 0.8 cc/g, and mostpreferably, greater than 1 cc/g.

[0086] The solid oxide compound should have a surface area from about100 m²/g to about 1000 m²/g, preferably from about 200 m²/g to about 800m²/g, and most preferably, from 200 m²/g to 800 m²/g.

[0087] The solid oxide compound can be made by any method known in theart. In a first method, the solid oxide compound can be made bycogellation of aqueous materials, as represented in U.S. Pat. Nos.3,887,494; 3,119,569; 4,405,501; 4,436,882; 4,436,883; 4,392,990;4,081,407; 4,981,831; and 4,152,503; the entire disclosures of which arehereby incorporated by reference. In this procedure, a titanium orzirconium salt, such as titanyl sulfate, is dissolved in an acid, suchas sulfuric acid, to which sodium silicate is added until gellationoccurs at neutral pH. Aging for several hours at about pH 7 to 10 and atabout 60 to about 90° C. is followed by washing and drying. Drying maybe accomplished by any means known in the art, such as, for example,azeotropic distillation, spray drying, flash drying, vacuum drying, andthe like.

[0088] In a second method, the solid oxide compound can be made bycogellation in an organic or anhydrous solution as represented by U.S.Pat. Nos. 4,301,034; 4,547,557; and 4,339,559; the entire disclosures ofwhich are hereby incorporated by reference. By these techniques, anorganic silicate, such as, for example, tetraethyl orthosilicate, and anorganic titanate or organic zirconate, such as, for example, titanium orzirconium tetraisopropoxide, is dissolved in an organic solution, suchas, for example, an alcohol, to which a small amount of water is addedalong with an acid or base to cause hydrolysis and gellation of thesolid oxide compound. The order of introduction of these ingredients canbe varied, and the addition of each can be divided into stages toachieve special properties. Aging and drying often result in a highporosity solid oxide compound.

[0089] In a third method, the solid oxide compound can be made bycoating the surface of silica with a layer of titania or zirconia, asexemplified by U.S. Pat. Nos. 4,424,320; 4,405,768; 4,402,864;4,382,022; 4,368,303; and 4,294,724; the entire disclosures of which arehereby incorporated by reference. Any technique known in the art can beused. One particularly common method is to treat a silica, which hasbeen dried at about 200° C. to remove adsorbed water, with an organicsolution of a titanium or zirconium alkoxide, such as, for example,titanium isopropoxide, or a titanium or zirconium halide, such as, forexample, titanium tetrachloride. Subsequent drying and calcining in airat high temperature converts the titanium or zirconium into titania orzirconia, which remains substantially dispersed. This reaction can alsobe accomplished in a gas phase if the titanium or zirconium compound isvaporized into a gas stream which is then allowed to contact the silica.

[0090] Any method known in the art for fluoriding the solid oxidecompound with a fluoride-containing compound can be used in thisinvention. One common way is to impregnate the solid oxide compound withan aqueous solution of a fluoride-containing salt, such as, for example,ammonium fluoride (NH₄F), ammonium bifluoride (HHF₂), hydrofluoric acid(HF), ammonium silicofluoride ((NH₄)₂SiF₆), ammonium fluoroborate(NH₄BF₄), ammonium fluorophosphate (NH₄PF₆), fluoroboric acid (HBF₄),and mixtures thereof. Alternatively, the fluoride-containing compoundcan be dissolved into an organic solvent, such as an alcohol, and usedto impregnate the solid oxide compound to minimize shrinkage of poresduring drying. Drying can be accomplished by any method known in the artsuch as vacuum drying, spray drying, flash drying, and the like.

[0091] The fluoride-containing compound can also be incorporated into agel by adding it to one of the aqueous materials before gellation. Theseaqueous materials were disclosed in the first and second methods forpreparing solid oxide compounds discussed previously in this disclosure.

[0092] The fluoride-containing compound can also be added to a slurrycontaining a gel before drying. Formation of a gel was disclosed in thefirst and second methods for preparing solid oxide compounds discussedpreviously in this disclosure.

[0093] The fluoride-containing compound can also be added duringcalcining. In this technique, the fluoride-containing compound isvaporized into a gas stream used to fluidize the solid oxide compound sothat it is fluorided from the gas stream. In addition to some of thefluoride-containing compounds described above, volatile organicfluorides may be used at temperatures above their decomposition points,or at temperatures high enough to cause reaction. For example,perfluorohexane, perfluorobenzene, trifluoroacetic acid, trifluoroaceticanhydride, hexafluoroacetylacetonate, and the like may be vaporized andcontacted with the solid oxide compound at about 300 to about 600° C. inair or nitrogen. Inorganic fluoride containing vapors may also be used,such as, for example, hydrogen fluoride or even elemental fluorine gas.

[0094] The solid oxide compound can also be calcined at a temperature ina range of about 100 to about 900° C. before being fluorided.

[0095] The amount of fluoride present before calcining is about 2 toabout 50% by weight fluoride based on the weight of the fluorided solidoxide compound before calcining. Preferably, it is about 3 to about 25%by weight, and most preferably, it is 4 to 20% by weight fluoride basedon the weight of the fluorided solid oxide compound before calcining.

[0096] It is important that the fluorided solid oxide compound becalcined. Generally, this calcining is conducted at a temperature in therange of about 200° C. to about 900° C., and for a time in the range ofabout 1 minute to about 100 hours. Preferably, the fluorided solid oxidecompound is calcined at temperatures from about 300° C. to about 700° C.and a time in the range of about 1 hour to about 50 hours, mostpreferably, temperatures from 350° C. to 600° C. and a time in the rangeof 3 to 20 hours.

[0097] Calcining can be completed in any suitable atmosphere. Generally,the calcining is completed in an inert atmosphere. Alternatively, thecalcining can be completed in an oxidizing atmosphere, such as, oxygenor air, or a reducing atmosphere, such as, hydrogen or carbon monoxide.Calcining can also be conducted in stages, for example, conducting thefluoriding in a gas phase at a lower temperature, then further calciningat a higher temperature. Alternatively, calcining can be conducted firstin an oxidizing atmosphere, then in a reducing atmosphere at a differenttemperature, or vice-versa.

[0098] Optionally, a small amount of chloride can be included in orafter the calcining treatment to achieve higher activity in some cases,or to increase the contribution of the titanium or zirconium.

[0099] The catalyst compositions of this invention can be produced bycontacting the organometal compound, the organoaluminum compound, andthe fluorided solid oxide compound, together. This contacting can occurin a variety of ways, such as, for example, blending. Furthermore, eachof these compounds can be fed into a reactor separately, or variouscombinations of these compounds can be contacted together before beingfurther contacted in the reactor, or all three compounds can becontacted together before being introduced into the reactor.

[0100] Currently, one method is to first contact the organometalcompound and the fluorided solid oxide compound together, for about 1minute to about 24 hours, preferably, 1 minute to 1 hour, at atemperature from about 10° C. to about 200° C., preferably 15° C. to 80°C., to form a first mixture, and then contact this first mixture with anorganoaluminum compound to form the catalyst composition.

[0101] Another method is to precontact the organometal compound, theorganoaluminum compound, and the fluorided solid oxide compound beforeinjection into a polymerization reactor for about 1 minute to about 24hours, preferably, 1 minute to 1 hour, at a temperature from about 10°C. to about 200° C., preferably 20° C. to 80° C.

[0102] A weight ratio of organoaluminum compound to the fluorided solidoxide compound in the catalyst composition ranges from about 5:1 toabout 1:1000, preferably, from about 3:1 to about 1:100, and mostpreferably, from 1:1 to 1:50.

[0103] A weight ratio of the fluorided solid oxide compound to theorganometal compound in the catalyst composition ranges from about10,000:1 to about 1:1, preferably, from about 1000:1 to about 10:1, andmost preferably, from 250:1 to 20:1. The ratios are based on the amountof the components combined to give the catalyst composition.

[0104] After contacting, the catalyst composition comprises apost-contacted organometal compound, a post-contacted organoaluminumcompound, and a post-contacted fluorided solid oxide compound. It shouldbe noted that the post-contacted fluorided solid oxide compound is themajority, by weight, of the catalyst composition. Often times, specificcomponents of a catalyst are not known, therefore, for this invention,the catalyst composition is described as comprising post-contactedcompounds.

[0105] A weight ratio of the post-contacted organoaluminum compound tothe post-contacted fluorided solid oxide compound in the catalystcomposition ranges from about 5:1 to about 1:1000, preferably, fromabout 3:1 to about 1:100, and most preferably, from 1:1 to 1:50.

[0106] A weight ratio of the post-contacted fluorided solid oxidecompound to the post-contacted organometal compound in the catalystcomposition ranges from about 10,000:1 to about 1:1, preferably, fromabout 1000:1 to about 10:1, and most preferably, from 250:1 to 20:1

[0107] The catalyst composition of this invention has an activitygreater than a catalyst composition that uses the same organometalcompound, and the same organoaluminum compound, but uses silica ortitania that has been impregnated with fluoride as shown in comparativeexamples 4 and 5. This activity is measured under slurry polymerizationconditions, using isobutane as the diluent, and with a polymerizationtemperature of about 50 to about 150° C., and an ethylene pressure ofabout 400 to about 800 psig. The reactor should have substantially noindication of any wall scale, coating or other forms of fouling.

[0108] However, it is preferred if the activity is greater than about1000 grams of polymer per gram of fluorided solid oxide compound perhour, more preferably greater than 2000, and most preferably greaterthan 2,500. This activity is measured under slurry polymerizationconditions, using isobutane as a diluent, and with a polymerizationtemperature of 90° C., and an ethylene pressure of 550 psig. The reactorshould have substantially no indication of any wall scale, coating orother forms of fouling.

[0109] One of the important aspects of this invention is that noaluminoxane needs to be used in order to form the catalyst composition.Aluminoxane is an expensive compound that greatly increases polymerproduction costs. This also means that no water is needed to help formsuch aluminoxanes. This is beneficial because water can sometimes kill apolymerization process. Additionally, it should be noted that no boratecompounds need to be used in order to form the catalyst composition. Insummary, this means that the catalyst composition, which isheterogenous, and which can be used for polymerizing monomers ormonomers and one or more comonomers, can be easily and inexpensivelyproduced because of the absence of any aluminoxane compounds or boratecompounds. Additionally, no organochromium compound needs to be added,nor any MgCl₂ needs to be added to form the invention. Althoughaluminoxane, borate compounds, organochromium compounds, or MgCl₂ arenot needed in the preferred embodiments, these compounds can be used inother embodiments of this invention.

[0110] In another embodiment of this invention, a process comprisingcontacting at least one monomer and the catalyst composition to produceat least one polymer is provided. The term “polymer” as used in thisdisclosure includes homopolymers and copolymers. The catalystcomposition can be used to polymerize at least one monomer to produce ahomopolymer or a copolymer. Usually, homopolymers are comprised ofmonomer residues, having 2 to about 20 carbon atoms per molecule,preferably 2 to about 10 carbon atoms per molecule. Currently, it ispreferred when at least one monomer is selected from the groupconsisting of ethylene, propylene, 1-butene, 3-methyl-1-butene,1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixturesthereof.

[0111] When a homopolymer is desired, it is most preferred to polymerizeethylene or propylene. When a copolymer is desired, the copolymercomprises monomer residues and one or more comonomer residues, eachhaving from about 2 to about 20 carbon atoms per molecule. Suitablecomonomers include, but are not limited to, aliphatic 1-olefins havingfrom 3 to 20 carbon atoms per molecule, such as, for example, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and otherolefins and conjugated or nonconjugated diolefins such as 1,3-butadiene,isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene,1,7-hexadiene, and other such diolefins and mixtures thereof. When acopolymer is desired, it is preferred to polymerize ethylene and atleast one comonomer selected from the group consisting of 1-butene,1-pentene, 1-hexene, 1-octene, and 1-decene. The amount of comonomerintroduced into a reactor zone to produce a copolymer is generally fromabout 0.01 to about 10 weight percent comonomer based on the totalweight of the monomer and comonomer, preferably, about 0.01 to about 5,and most preferably, 0.1 to 4. Alternatively, an amount sufficient togive the above described concentrations, by weight, in the copolymerproduced can be used.

[0112] Processes that can polymerize at least one monomer to produce apolymer are known in the art, such as, for example, slurrypolymerization, gas phase polymerization, and solution polymerization.It is preferred to perform a slurry polymerization in a loop reactionzone. Suitable diluents used in slurry polymerization are well known inthe art and include hydrocarbons which are liquid under reactionconditions. The term “diluent” as used in this disclosure does notnecessarily mean an inert material; it is possible that a diluent cancontribute to polymerization. Suitable hydrocarbons include, but are notlimited to, cyclohexane, isobutane, n-butane, propane, n-pentane,isopentane, neopentane, and n-hexane. Furthermore, it is most preferredto use isobutane as the diluent in a slurry polymerization. Examples ofsuch technology can be found in U.S. Pat. Nos. 4,424,341; 4,501,885;4,613,484; 4,737,280; and 5,597,892; the entire disclosures of which arehereby incorporated by reference.

[0113] The catalyst compositions used in this process produce goodquality polymer particles without substantially fouling the reactor.When the catalyst composition is to be used in a loop reactor zone underslurry polymerization conditions, it is preferred when the particle sizeof the solid oxide compound is in the range of about 10 to about 1000microns, preferably about 25 to about 500 microns, and most preferably,50 to 200 microns, for best control during polymerization.

[0114] In a specific embodiment of this invention, a process is providedto produce a catalyst composition, the process comprising (optionally,“consisting essentially of”, or “consisting of”):

[0115] (1) contacting a solid oxide compound with water containingammonium bifluoride to produce a fluorided solid oxide compound;

[0116] wherein the solid oxide compound is selected from the groupconsisting of silica-titania and silica-zirconia;

[0117] (2) calcining the fluorided solid oxide compound at a temperaturewithin a range of 350 to 600° C. to produce a calcined compositionhaving 4 to 20 weight percent fluoride based on the weight of thefluorided solid oxide compound before calcining;

[0118] (3) combining the calcined composition andbis(n-butylcyclopentadienyl)zirconium dichloride at a temperature withinthe range of 15° C. to 80° C. to produce a mixture; and

[0119] (4) after between 1 minute and 1 hour, combining the mixture andtriethylaluminum to produce the catalyst composition.

[0120] Hydrogen can be used in this invention in a polymerizationprocess to control polymer molecular weight.

[0121] One of the features of this invention is that the fluorided solidoxide compound activates the organometal compound much more efficientlythan silica, silica-titania, or silica-zirconia alone. Thus, the titaniaor zirconia contributes to the activation of the organometal compound. Asecond feature of this invention is that the titania or zirconia is aweak polymerization catalyst in its own right, providing a highmolecular weight component onto an otherwise symmetrical molecularweight distribution of the polymer produced by the organometal compound.This high molecular weight component, or skewed molecular weightdistribution, imparts higher melt strength and shear response to thepolymer than could be obtained from typical organometal compounds. Thesepolymers may vary in molecular weight distribution depending on theorganometal compound used and the relative contribution of the titaniumor zirconium. One special feature of this invention, therefore, is thatpolydispersities of about 2.5 to about 4.0 and HLMI/MI values from about25 to about 50 can be produced from organometal compounds that wouldotherwise give polydispersities of about 2.1 to about 2.5 and HLMI/MIvalues less than about 20.

[0122] After the polymers are produced, they can be formed into variousarticles, such as, for example, household containers and utensils, filmproducts, drums, fuel tanks, pipes, geomembranes, and liners. Variousprocesses can form these articles. Usually, additives and modifiers areadded to the polymer in order to provide desired effects. It is believedthat by using the invention described herein, articles can be producedat a lower cost, while maintaining most, if not all, of the uniqueproperties of polymers produced with organometal compounds.

EXAMPLES

[0123] Test Methods

[0124] A “Quantachrome Autosorb-6 Nitrogen Pore Size DistributionInstrument” was used to determined the surface area and pore volume ofthe supports. This instrument was acquired from the QuantachromeCorporation, Syosset, N.Y.

[0125] Polymer density was determined in grams per cubic centimeter(g/cc) on a compression molded sample, cooled at about 15° C. per hour,and conditioned for about 40 hours at room temperature in accordancewith ASTM D1505 and ASTM D1928, Procedure C.

[0126] High load melt index (HLMI, g/10 mins) was determined inaccordance with ASTM D1238 at 190° C. with a 21,600 gram weight.

[0127] Melt index (MI, g/10 mins) was determined in accordance with ASTMD1238 at 190° C. with a 2,160 gram weight.

[0128] Description of Polymerizations Runs:

[0129] Polymerization runs were made in a 2.2 liter steel reactorequipped with a marine stirrer running at 400 revolutions per minute(rpm). The reactor was surrounded by a steel jacket containing boilingmethanol with a connection to a steel condenser. The boiling point ofthe methanol was controlled by varying nitrogen pressure applied to thecondenser and jacket, which permitted precise temperature control towithin half a degree centigrade, with the help of electronic controlinstruments.

[0130] Unless otherwise stated, first a small amount (0.01 to 0.10 gramsnormally) of an oxide compound or the inventive fluorided solid oxidecompound was charged under nitrogen to a dry reactor. Next, twomilliliters of an organometal compound solution containing 0.5 grams ofan organometal compound (usually bis(n-butlycyclopentadienyl)zirconiumdichloride) per 100 milliliters of toluene was added by syringe. Then,1.2 liters of isobutane liquid were charged to a reactor, and thereactor heated up to 90° C. One milliliter or two milliliters to TEA asa 15 weight % (1 molar) solution in heptane or ethyl aluminum dichloride(EADC) as a 25 weight % (1.5 molar) solution in heptane was added midwayduring the isobutane addition. Finally, ethylene was added to thereactor to equal a fixed pressure, normally 550 psig, which wasmaintained during the experiment. The stirring was allowed to continuefor the specified time, usually around one hour, and the activity wasnoted by recording the flow of ethylene into the reactor to maintainpressure.

[0131] After the allotted time, the ethylene flow was stopped, and thereactor slowly depressurized and opened to recover a granular polymer.In all cases, the reactor was clean with no indication of any wallscale, coating or other forms of fouling. The polymer was then removedand weighed.

Comparative Examples 1 & 2

[0132] (No Oxide Compound):

[0133] This example demonstrates that an organometal compound solutionadded to a reactor with an organoaluminum compound but with no oxidecompound does not provide any activity. A polymerization run was made asdescribed previously. First, 2 milliliters ofbis(n-butylcyclopentadienyl)zirconium dichloride solution (0.5 grams ofbis(n-butylcylopentadienyl)zirconium dichloride per 100 ml of toluene)were added. Then, half of the one liter of isobutane was added followedby 2 milliliters of 15% by weight TEA in example 1 or 2 milliliters of25% ethylaluminum dichloride (EADC) in example 2. The other half of theisobutane was added, and finally, ethylene was added. No activity wasobserved. After one hour of stirring, the reactor was depressurized andopened, but in each case, no polymer was found. These results are shownin Table 1.

Comparative Example 3

[0134] (Silica):

[0135] This example demonstrates the use of silica as-an activator foran organometal compound when used with an organoaluminum compound.

[0136] Silica was obtained from W. R. Grace, grade 952, having a porevolume of about 1.6 cc/g and a surface area of about 300 square metersper gram. About 10 grams of the silica were placed in a 1.75 inch quartztube fitted with a sintered quartz disk at the bottom. While the silicawas supported on the disk, dry air was blown up through the disk at thelinear rate of about 1.6 to 1.8 standard cubic feet per hour. Anelectric furnace around the quartz tube was then turned on, and thetemperature was raised at the rate of 400° C. per hour to a temperatureof 600° C. At this temperature, the silica was allowed to fluidize forthree hours in the dry air to produce a calcined silica. Afterward, thesilica was collected and stored under dry nitrogen. It did not have anyexposure to the atmosphere.

[0137] The calcined silica was then added to the reactor, followed by anorganometal compound solution and TEA solution as described previously.These runs are shown in Table 1, which lists the amount of calcinedsilica charged, the run time in minutes, and the amount of polymerproduced. The calcined silica produced almost no polymer.

Comparative Example 4

[0138] (Fluorided Silica)

[0139] A 50 gram sample of grade 952 silica described previously wasimpregnated with 100 milliliters of an aqueous solution containing 5grams of dissolved ammonium bifluoride to produce a fluorided silica.This gave the sample a wet sand consistency which was then dried underhalf an atmosphere of vacuum at 110° C. overnight. Then, the fluoridedsilica was calcined in dry air at 600° C. by the procedures described inExample 3. The fluorided silica had a surface area of about 192 squaremeters per gram and a pore volume of about 1.29 cc/g.

[0140] A small sample of this fluorided silica was then tested as anactivator for an organometal compound and an organoaluminum compound ina polymerization experiment. As shown in Table 1, it provided noactivity.

Comparative Example 5

[0141] (Fluorided Titania)

[0142] A 5 gram sample of Aerosil titania was obtained from Degussa,Inc. and calcined in dry air at 600° C. for three hours as described inExample 3. During this calcining, one milliliter of perfluorohexane wasinjected into a gas stream upstream from the titania bed. As theperfluororhexane vapor rose into the 600° C. bed, it decomposed, thuslaying down fluoride onto the surface of the titania. This produced afluorided titania.

[0143] A small sample of this fluorided titania was then tested as anactivator for an organometal compound in a polymerization experiment. Asshown in Table 1, it provided almost no activity.

Comparative Example 6

[0144] (Silica-Titania)

[0145] A silica-titania was prepared by cogellation as described inDeitz, U.S. Pat. No. 3,887,494. Titanyl sulfate was dissolved inconcentrated sulfuric acid, to which a sodium silicate solution wasadded slowly with vigorous stirring. When the pH reached about 6, themixture gelled into a homogenous clear mass. This was then aged at 80°C. at pH 7 for three hours, then washed nine times with water and twotimes in 1% by weight ammonium nitrate. This gel was then azeotropicallydried in ethyl acetate to produce a silica-titania. The silica-titaniacontained about 8% titanium and had a surface area of about 450 squaremeters per gram and pore volume of about 2.0 cc/g. A 10 gram sample ofthe silica-titania was then calcined at 600° C. for three hours influidizing dry air. Afterward, a small sample of the silica-titania wastested for polymerization activity with an organometal compoundsolution. As shown in Table 1, it exhibited no appreciable activity.

Inventive Example 7

[0146] (Fluorided Silica-Titania Calcined at 600° C.)

[0147] A sample of 8.51 grams of the silica-titania from Example 5 wascalcined by fluidizing in dry air at 600° C. for three hours. Then, itwas impregnated with 35 milliliters of a solution made by dissolving2.50 grams of ammonium bifluoride in 100 milliliters of methanol. Thisbrought the silica-titania to incipient wetness and constituted anequivalent of about 3.9 millimoles of fluoride per gram to produce afluorided silica-titania. The methanol was then evaporated off, and thefluorided silica-titania was again calcined in air at 600° C. for threehours as described above.

[0148] Then, 0.1166 grams of the fluorided silica-titania were firstcharged under nitrogen to a dry reactor. Next, two milliliters of anorganometal compound solution containing 0.5 grams ofbis(n-butlycyclopentadienyl)zirconium dichloride per 100 milliliters oftoluene was added by syringe. Then, 1.2 liters of isobutane liquid wascharged, and the reactor brought up to 90° C. One milliliter of 15% TEAwas added midway during the isobutane addition. Finally, ethylene wasadded to the reactor to equal 550 psig pressure which was maintainedduring the experiment. The stirring was allowed to continue for onehour, and the activity was noted by recording the flow of ethylene intothe reactor to maintain pressure.

[0149] After the allotted time, the ethylene flow was stopped, and thereactor slowly depressurized and opened to recover a granular polymer.The reactor was clean with no indication of any wall scale, coating orother forms of fouling. The polymer was removed and weighed yielding137.5 grams. Thus, the activity was found to be 1164 grams of polymerproduced per gram of fluorided silica-titania charged per hour. The dataare shown in Table 1.

[0150] The polymer had a broader molecular weight distribution thanpolymers produced by typical organometal compounds. It had a melt indexof 0.04 g/10 min and a high load melt index of 1.72 g/10 min, giving ashear ratio of 42.5, which is higher than the usual 16-17 ratio obtainedfrom typical organometal compounds. The number average molecular weightwas found to be 66,000, and the weight average was 178,000, giving apolydispersity (Mw/Mn) of 2.7. These data are shown in Table 2.

Inventive Examples 8 & 9

[0151] (Fluorided Silica-Titania Calcined at 450° C.)

[0152] Another sample of the fluorided silica-titania described inExample 7 was calcined at 450° C. instead of 600° C. It too was testedin a polymerization run, and the activity was found to increase to 1834grams of polymer obtained per gram of fluorided silica-titania chargedper hour (Table 1, Example 8).

[0153] This fluorided silica-titania that was calcined at 450° C. wastested again, except that it was allowed to react with the TEA and theorganometal compound at 90° C. in a reactor for 20 minutes beforeethylene was added. This step increased the measured activity to 2837grams polymer per gram of fluorided silica-titania per hour (Table 1,Example 9).

Comparative Examples 10 & 11

[0154] ( Silica-Zirconia)

[0155] A silica-zirconia was prepared by the following procedure. Asilica obtained from W. R. Grace as grade 952 was obtained having asurface area of about 300 square meters per gram and a pore volume ofabout 1.6 cc/g. A 26.3 gram sample of silica was dried for three hoursat 200° C. in fluidizing nitrogen. Afterward, 50 milliliters of aheptane solution containing 11.72 grams of zirconium propoxide wereadded to the sample. The heptane was then evaporated under nitrogen at60 degrees C. until the sample was dry to produce a silica-zirconia. Itwas then calcined in air at 600° C. for three hours. In two tests, thepolymerization activity of this silica-zirconia was found to produce 35and 78 grams of polymer per gram of silica-zirconia per hour.

Inventive Example 12

[0156] (Fluorided Silica-Zirconia)

[0157] The silica-zirconia used in Examples 10 and 11 was then fluoridedby the following procedure. 14.3 grams of the silica-zirconia, which hadalready been calcined at 600° C., were saturated with an aqueoussolution containing 0.82 grams of ammonium bifluoride, which yielded afluorided silica-zirconia having a wet sand consistency. The fluoridedsilica-zirconia was dried under vacuum at 120° C. overnight, thencalcined in dry air at 500° C. for three hours before being tested foractivity. The activity increased to 465 grams of polymer produced pergram of silica-zirconia per hour.

Comparative Example 13

[0158] (Silica-Zirconia)

[0159] A silica-zirconia containing 10 weight percent zirconium wasprepared by anhydrous gellation as detailed by the following procedure.One mole (about 200 mls) of tetraethyl orthosilicate was added to 500milliliters of n-propanol. One milliliter of sulfuric acid was thenadded along with 30 milliliters of water, which is about 85% of theamount required for complete hydrolysis. This solution was stirred forthirty minutes to allow for reaction. It warmed slightly, indicatingthat hydrolysis was taking place. Then, 71 milliliters of zirconiumpropoxide were added, but no precipitation of zirconia took place,indicating that substantially all of the water had been consumed byreaction with the tetraethyl orthosilicate. The solution was stirred 15minutes, and the another 50 milliliters of water was added, but again,no zirconia precipitated, indicating that it had become incorporatedinto the silica. The solution was allowed to stir another 15 minutes,then ammonium hydroxide was added until gellation occurred causing aclear gel to form. The gel was dried in a vacuum oven at 120° C.overnight, then a sample was calcined in dry air at 600° C. for threehours. This sample produced an activity of 230 grams of polymer per gramof silica-zirconia per hour when tested for polymerization activity withan organometal compound and an organoaluminum compound.

Inventive Examples 14 & 15

[0160] (Fluorided Silica-Zirconia)

[0161] Two samples of the silica-zirconia described in Example 12, oneobtained before being calcined at 600° C. (Example 14) and the otherobtained afterward (Example 15), were impregnated with a methanolsolution containing enough ammonium bifluoride to equal 10% of theweight of the sample. Both samples were dried at 120° C. overnight undervacuum, then calcined at 500° C. for three hours in air. When tested forpolymerization activity with an organometal compound and anorganoaluminum compound, both yielded a high activity of between 3000and 5000 grams of polymer per gram of fluorided silica-zirconia perhour. TABLE 1 Polymerization Results Test Organo- Calcining CompoundAluminum Test* Temp. Charged Compound Polymer Run Time Activity* ExampleCompound (° C.) (g) (mmol) (g) (min) (g/g/h) 1-Control No Oxide 0.0000 2TEA 0 61.1 0 Compound 2-Control No Oxide 0.0000 2 EADC 0 28.0 0 Compound3-Control Silica 600 0.5686 2 TEA 0.7 63.0 1 4-Control Fluorided 6000.4350 1 TEA 0 24.5 0 Silica 5-Control Fluorided 600 0.1461 1 TEA 0.234.1 2 Titania 6-Control Silica-Titania 600 0.1392 2 TEA 0 60.0 07-Inventive Fluorided 600 0.1166 1 TEA 135.7 60.0 1164 Silica-Titania8-Inventive Fluorided 450 0.0090 1 TEA 17.0 61.8 1834 Silica-Titania9-Inventive Fluorided 450 0.1893 1 TEA 179.0 20.0 2837 Silica-Titania10-Control Silica-Zirconia 600 0.1663 1 TEA 13.0 60.0 78 11-ControlSilica-Zirconia 600 0.2493 1 TEA 6.0 41.5 35 12-Inventive Fluorided 5000.2108 1 TEA 98.0 60.0 465 Silica-Zirconia 13-Control Silica-Zirconia600 0.2229 1 TEA 67.8 58.0 230 14-Inventive Fluorided 500 0.0277 1 TEA98.0 70.0 3033 Silica-Zirconia 15-Inventive Fluorided 500 0.1129 1 TEA257.0 30.9 4420 Silica-Zirconia

[0162] TABLE 2 Number Weight Avg. Test HLMI Avg. Mol. Mol. Wt. Compound(g/10 min) HLMI/MI Wt. (Mn) (Mn) Mw/Mn Fluorided 1.72 42.5 66,000178,000 2.7 Silica-titania

[0163] While this invention has been described in detail for the purposeof illustration, it is not intended to be limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed is:
 1. A process to produce a catalystcomposition, said process comprising contacting an organometal compound,an organoalunrinum compound, and a fluorided solid oxide compound toproduce said catalyst composition, wherein said organometal compound hasthe following general formula: (X¹)(X²)(X³)(X⁴)M¹ wherein M¹ is selectedfrom the group consisting of titanium, zirconium, and hafnium; wherein(X¹) is independently selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls; wherein substituentson said substituted cyclopentadienyls, substituted indenyls, andsubstituted fluorenyls of (X¹) are selected from the group consisting ofaliphatic groups, cyclic groups, combinations of aliphatic and cyclicgroups, silyl groups, alkyl halide groups, halides, organometallicgroups, phosphorus groups, nitrogen groups, silicon, phosphorus, boron,germanium, and hydrogen; wherein at least one substituent on (X¹) can bea bridging group which connects (X¹) and (X²); wherein (X³) and (X⁴) areindependently selected from the group consisting of halides, aliphaticgroups, substituted aliphatic groups, cyclic groups, substituted cyclicgroups, combinations of aliphatic groups and cyclic groups, combinationsof substituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic groups and substituted cyclic groups, amidogroups, substituted amido groups, phosphido groups, substitutedphosphido groups, alkyloxide groups, substituted alkyloxide groups,aryloxide groups, substituted aryloxide groups, organometallic groups,and substituted organometallic groups; wherein (X²) is selected from thegroup consisting of cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, substituted fluorenyls,halides, aliphatic groups, substituted aliphatic groups, cyclic groups,substituted cyclic groups, combinations of aliphatic groups and cyclicgroups, combinations of substituted aliphatic groups and cyclic groups,combinations of aliphatic groups and substituted cyclic groups,combinations of substituted aliphatic groups and substituted cyclicgroups, amido groups, substituted amido groups, phosphido groups,substituted phosphido groups, alkyloxide groups, substituted alkyloxidegroups, aryloxide groups, substituted aryloxide groups, organometallicgroups, and substituted organometallic groups; wherein substituents on(X²) are selected from the group consisting of aliphatic groups, cyclicgroups, combinations of aliphatic groups and cyclic groups, silylgroups, alkyl halide groups, halides, organometallic groups, phosphorusgroups, nitrogen groups, silicon, phosphorus, boron, germanium, andhydrogen; wherein at least one substituent on (X²) can be a bridginggroup which connects (X¹) and (X²); wherein said organoaluminum compoundhas the following general formula: Al(X⁵)_(n)(X⁶)_(3−n) wherein (X⁵) isa hydrocarbyl having from 1 to about 20 carbon atoms; wherein (X⁶) is ahalide, hydride, or alkoxide; and wherein “n” is a number from 1 to 3inclusive; and wherein said fluorided solid oxide compound comprisesfluoride and a solid oxide compound; wherein said solid oxide compoundis selected from the group consisting of silica-titania andsilica-zirconia.
 2. A process comprising: 1) contacting a solid oxidecompound with water containing ammonium bifluoride to produce afluorided solid oxide compound; wherein said solid oxide compound isselected from the group consisting of silica-titania andsilica-zirconia; 2) calcining said fluorided solid oxide compound at atemperature within a range of 350 to 600° C. to produce a calcinedcomposition having 4 to 20 weight percent fluoride based on the weightof said fluorided solid oxide compound before calcining; 3) combiningsaid calcined composition and bis(n-butylcyclopentadienyl)zirconiumdichloride at a temperature within the range of 15° C. to 80° C. toproduce a mixture; and 4) after between 1 minute and 1 hour, combiningsaid mixture and triethylaluminum to produce said catalyst composition.3. A process according to claim 2 wherein said process consistsessentially of steps (1), (2), (3), and (4).
 4. A catalyst compositionproduced by the process of claim
 1. 5. A catalyst composition accordingto claim 4 wherein said catalyst composition has an activity greaterthan about 1000 grams of polymer per gram of fluorided solid oxidecompound per hour under slurry polymerization conditions, usingisobutane as a diluent, with a polymerization temperature of 90° C., andan ethylene pressure of 550 psig.
 6. A catalyst composition according toclaim 5 wherein said catalyst composition has an activity greater thanabout 2500 grams of polymer per gram of fluorided solid oxide compoundper hour under slurry polymerization conditions, using isobutane as adiluent, with a polymerization temperature of 90° C., and an ethylenepressure of 550 psig.
 7. A catalyst composition according to claim 5wherein a weight ratio of said organoaluminum compound to said fluoridedsolid oxide compound in said catalyst composition ranges from about 3:1to about 1:100.
 8. A catalyst composition according to claim 7 whereinsaid weight ratio of said organoaluminum compound to said fluoridedsolid oxide compound in said catalyst composition ranges from 1:1 to1:50.
 9. A catalyst composition according to claim 5 wherein a weightratio of said fluorided solid oxide compound to said organometalcompound in said catalyst composition ranges from about 1000:1 to about10:1.
 10. A catalyst composition according to claim 9 wherein saidweight ratio of said fluorided solid oxide compound to said organometalcompound in said catalyst composition ranges from 250:1 to 20:1.
 11. Acatalyst composition comprising a post-contacted organometal compound, apost-contacted organoaluminum compound, and a post-contacted fluoridedsolid oxide compound.
 12. A polymerization process comprising contactingat least one monomer and said catalyst composition of claim 4 underpolymerization conditions to produce at least one polymer.
 13. A processaccording to claim 12 wherein said polymerization conditions compriseslurry polymerization conditions.
 14. A process according to claim 13wherein said contacting is conducted in a loop reaction zone.
 15. Aprocess according to claim 14 wherein said contacting is conducted inthe presence of a diluent that comprises, in major part, isobutane. 16.A process according to claim 12 wherein said at least one monomer isethylene.
 17. A process according to claim 12 wherein said at least onemonomer comprises ethylene and an aliphatic 1-olefin having 3 to 20carbon atoms per molecule.
 18. A polymer produced in accordance with theprocess of claim
 12. 19. A polymer produced according to claim 12wherein said polymer has a polydispersity ranging from about 2.5 to 4.0and a shear ratio (HLMI/MI) ranging from about 25 to about
 50. 20. Anarticle produced from the polymer of claim 18.